In a photoresist step as one of semiconductor manufacturing steps, a resist is conventionally applied to a surface of a semiconductor wafer (hereinafter referred to as “wafer”) which is a substrate, and the wafer is developed after an exposure process so as to form a resist pattern in the surface. Such a series of processes is generally performed by a system in which an exposure apparatus is connected to an application and development apparatus configured to apply and develop a resist.
In the developing process in the series of processes, a developer is supplied onto a wafer, and then the wafer is kept in a stationary state for a predetermined period, for example, so that a soluble region of the resist is dissolved to form a pattern. Thereafter, a cleaning process is performed for removing the dissolved matters of the resist together with the developer from a surface of the wafer. As a conventional cleaning method, a cleaning liquid is supplied to a central part of the wafer, a film of the cleaning liquid is spread by a centrifugal force, and the dissolved matters and the developer are removed from the wafer by means of the liquid-film flow.
However, there is a possibility that the dissolved matters (dissolved products) cannot be fully eliminated by the spin cleaning method. When a line width of the pattern is wide, the spin cleaning method poses no problem. However, when a line width thereof is narrow, it is highly possible that some remaining dissolved products may appear (remain) as development faults. Thus, in the present circumstances, the spin cleaning is performed for as long as 60 seconds, for example. However, even when the spin-cleaning process is performed for such a long time, some dissolved products may be left, i.e., a desired perfect cleaning may not be performed.
Thus, the Applicant of this patent application has proposed a method in which a cleaning liquid is discharged from a cleaning-liquid nozzle to a central part of a wafer that is being rotated, the cleaning-liquid nozzle is then slightly moved outward the wafer, an N2 gas is discharged from a gas nozzle to the central part of the wafer so as to form a core of a dried area, and then the cleaning-liquid nozzle is moved further outward the wafer while discharging the cleaning liquid such that the cleaning-liquid nozzle is not caught up with the spreading dried area (JP2006-80315A (particularly FIG. 7, and paragraphs 0040 and 0043) (Patent Document 1)). This method is advantageous in that a high cleaning effect can be obtained, and the cleaning process can be performed for a shorter period.
On the other hand, since a device pattern has been more and more miniaturized and also a film has been more and more thinned, a resolution of exposure is required to be raised. Thus, in order to further improve an exposure technique using an existing light source, such as argon fluoride (ArF) and krypton fluoride (KrF), so as to raise the resolution, it is under review that a substrate is exposed with a light-transmittable liquid phase being formed on a surface of the substrate (this method is hereinafter referred to as “immersion exposure process”). The immersion exposure process, in which a light is transmitted through extrapure water, for example, takes advantage of the fact that a wavelength becomes shorter in the water, e.g., a 193-nm wavelength of the ArF becomes substantially a 134-nm wavelength in the water.
One of problems of this immersion exposure process is that there is a possibility that a wafer on which water droplets remain may be transferred from an exposure apparatus to an application and development apparatus. An exposed wafer is subjected to a thermal process. In this case, presence of the water droplets on the wafer, or presence of so-called water marks, which are water stains generated by the dried water droplets, may adversely affect the resolution of a pattern directly below the water droplets or the water marks. Thus, it is necessary to clean the surface of the exposed wafer so as to remove the water droplets.
In the immersion exposure process, in order to improve a scanning and tracking property of an immersion part (tip end of the lens) of an exposure apparatus so as to secure a throughput equivalent to that of a conventional exposure apparatus, it is under review that there is formed on the exposed wafer surface a highly water-repellent protective film whose static contact angle with respect to water is between, e.g., about 75 and 85 degrees. However, it is all the more likely that small water droplets remain on a surface of the protective film because of the high water repellency of the protective film. The static contact angle with respect to water is defined as follows. As shown in FIG. 25, when a water droplet adhering to a surface of a substrate is viewed in its cross-section, an outer edge of the water droplet is viewed as an arc. The static contact angle with respect to water is an angle θ which is defined between a tangent of the arc on the surface of the substrate and the surface itself. The static contact angle with respect to water may be lowered by a developing process. Herebelow, the simple term “contact angle” means the static contact angle, and more specifically the term means a static contact angle with respect to water before a substrate is subjected to a developing process.
In a scanning process by the immersion part, when particles remain on the surface of the substrate, the particles may be taken into a liquid existing under the immersion part, resulting in development faults. That is, development faults may be caused by the particles in respective scanning positions. Thus, before the immersion exposure step, it is necessary to clean the wafer surface so as to perfectly remove the particles. However, in the method of the Patent Document 1, since a contact angle of the surface with respect to the wafer is large, i.e., the surface has a high water repellency, it is difficult to fully remove the particles (before the immersion exposure process) or water droplets (after the immersion exposure process) in an area remote from a central part of the wafer.
The reason therefor is described with reference to FIG. 26A and FIG. 26B. As shown in FIG. 26A, a cleaning liquid R is firstly discharged from a cleaning-liquid nozzle 11 to a center of a wafer W and the cleaning liquid R is spread all over the surface of the wafer W. Then, as shown in FIG. 26B, an N2 gas is discharged from a gas nozzle 12 to form a core of a dried area on the central part of the wafer W. At this time, since the water repellency of the surface of the wafer W is high, a thin liquid film moves outward at a considerably high speed. Thus, the thin liquid film is torn into water droplets M which then may remain on the surface. In an area near to the center of the wafer W, since the cleaning liquid R is discharged to the central part of the wafer W, and a centrifugal force in this area is smaller, a cleaning efficiency is high in this area, whereby substantially no water droplet remains in this area.
In addition, it is under review that a more water-repellent (more hydrophobic) resist film (whose static contact angle with respect to water is 85 degrees or more) is used instead of the protective film. When such a resist is used, the water repellency of the surface of the wafer is still high even after a development process. This gives rise to the following problem in the method of the Patent Document 1.
In a case in which a water repellency of the surface of the wafer is not so high, i.e., a contact angle with respect to water is not so large, when the dried core is formed and spread after the cleaning liquid has been discharged to the central part of the wafer and spread all over the surface of the wafer, as shown in FIG. 27A, the cleaning liquid R remaining in a recess 13 of the resist pattern is taken by the cleaning liquid moving outward the wafer along the patterned surface outside the recess 13, so that the cleaning liquid is discharged from the recess 13. On the other hand, in a case in which a contact angle with respect to water on the surface of the wafer is as large as 85 degrees, the speed at which the dried core is spread becomes considerably fast, namely, the speed at which the thin liquid film on the patterned surface moves outward the wafer becomes considerably fast. Thus, as shown in FIG. 27B, the cleaning liquid R in the recess 13 is torn from the liquid film and is left in the recess 13. Since this cleaning liquid R contains dissolved products of the resist, the cleaning liquid R causes a development fault. Although this development fault scarcely occurs in an area near to the center of the wafer, which is described above, the number of development faults noticeably increases in an area outside the area that is near to the center of the wafer.
Further, WO2005-50724 (particularly, FIG. 7, and paragraphs 0040 and 0043) (patent document 2) describes a cleaning method in which a process-liquid nozzle is moved at a high speed from a center of a wafer to a position distant therefrom by 10 mm to 15 mm, an N2 gas is promptly ejected from an N2 nozzle to the central part of the wafer so as to facilitate drying of the central part of the wafer, and the process-liquid nozzle is caused to scan toward a periphery of the wafer at a speed of 3 mm/second or less. However, the Patent Document 2 does not describe a technique for reliably cleaning the overall surface of the wafer, i.e., from an area near to the central part of the wafer to a periphery thereof, when the surface of the wafer has a contact angle of as large as 85 degrees or more. Specifically, there may arise problems in that the dried area may not be suitably formed depending on sizes of the cleaning-liquid nozzle and the gas nozzle and/or in that the nozzle-movement speed is so slow that the process period is long.